1、Designation: E 439 04aStandard Test Methods forChemical Analysis of Beryllium1This standard is issued under the fixed designation E 439; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parenth
2、eses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 These test methods cover the chemical analysis ofberyllium having chemical compositions within the followinglimits:ConcentrationElement Range, %Aluminu
3、m 0.05 to 0.30Beryllium 97.5 to 100Beryllium Oxide 0.3 to 3Carbon 0.05 to 0.30Copper 0.005 to 0.10Chromium 0.005 to 0.10Iron 0.05 to 0.30Magnesium 0.02 to 0.15Nickel 0.005 to 0.10Silicon 0.02 to 0.151.2 The test methods in this standard are contained in thesections indicated below.SectionsChromium b
4、y the Diphenylcarbazide Photometric Test Method0.004 to 0.04 % 10-19Iron by the 1,10-Phenanthroline Photometric Test Method 0.05 to0.25 % 20-29Manganese by the Periodate Photometric Test Method 0.008 to0.04 % 30-39Nickel by the Dimethylglyoxime Photometric Test Method 0.001 to0.04 % 40-491.3 This st
5、andard does not purport to address all of thesafety problems, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1
6、 ASTM Standards:2D 1193 Specification for Reagent WaterE 29 Practice for Using Significant Digits in Test Data toDetermine Conformance with SpecificationsE 50 Practices for Apparatus, Reagents, and Safety Precau-tions for Chemical Analysis of MetalsE 55 Practice for Sampling Wrought Nonferrous Metal
7、s andAlloys for Determination of Chemical CompositionE 60 Practice for Photometric and SpectrophotometricMethods for Chemical Analysis of MetalsE 88 Practice for Sampling Nonferrous Metals and Alloysin Cast Form for Determination of Chemical CompositionE 135 Terminology Relating to Analytical Chemis
8、try forMetals, Ores, and Related MaterialsE 173 Practice for Conducting Interlaboratory Studies ofMethods for Chemical Analysis of Metals3E 1601 Practice for Conducting an Interlaboratory Study toEvaluate the Performance of an Analytical Method3. Terminology3.1 For definitions of terms used in this
9、test method, refer toTerminology E 135.4. Significance and Use4.1 These test methods for the chemical analysis of beryl-lium metal are primarily intended as referee methods to testsuch materials for compliance with compositional specifica-tions. It is assumed that all who use these test methods will
10、 betrained analysts capable of performing common laboratoryprocedures skillfully and safely. It is expected that work will beperformed in a properly equipped laboratory.5. Apparatus, Reagents, and Photometric Practice5.1 Apparatus and reagents required for each determinationare listed in separate se
11、ctions preceding the procedure unlessotherwise specified. The apparatus, standard solutions, andreagents shall conform to the requirements prescribed inPractices E 50. Photometers shall conform to the requirementsprescribed in Practice E 60.5.2 Photometric and spectrophotometric practice prescribedi
12、n these test methods shall conform to Practice E 60.6. Hazards6.1 For precautions to be observed in these test methods,reference shall be made to Practices E 50. Both beryllium1These test methods are under the jurisdiction of ASTM Committee E01 onAnalytical Chemistry for Metals, Ores, and Related Ma
13、terials and are the directresponsibility of Subcommittee E01.05 on Cu, Pb, Zn, Cd, Sn, Be, their Alloys andRelated Metals.Current edition approved October 1, 2004. Published November 2004. Originallypublished in 1971. Last previous edition approved in 2004 as E 439 04.2For referenced ASTM standards,
14、 visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Withdrawn. Available from Global Engineering, 15 Inverness Way East,Englewood, CO 80112.1Co
15、pyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.metal and its compounds may be toxic. Care should beexercised to prevent contact of beryllium-containing materialswith the skin. The inhalation of any beryllium-containingsubstance, either
16、 as a volatile compound or as finely dividedpowder, should be especially avoided. Beryllium-containingresidues (especially ignited oxide) should be carefully disposedof.7. Sampling7.1 Wrought products shall be sampled in accordance withPractice E 55. Cast products shall be sampled in accordancewith
17、Practice E 88. However, these test methods do notsupersede any sampling requirements specified in a specificASTM material specification.8. Rounding Calculated Values8.1 Calculated values shall be rounded to the desired num-ber of places as directed in Practice E 29.9. Interlaboratory Studies9.1 Thes
18、e test methods have been evaluated in accordancewith Practices E 173, unless otherwise noted under the preci-sion section.CHROMIUM BY THE DIPHENYLCARBAZIDE(PHOTOMETRIC) TEST METHOD10. Scope10.1 This test method covers the determination of chro-mium in concentrations from 0.004 to 0.04 %.11. Summary
19、of Test Method11.1 Chromium is oxidized by peroxydisulfate in the pres-ence of silver nitrate, and the chromium diphenylcarbazidecomplex is then developed. Photometric measurement is madeat approximately 540 nm.12. Concentration Range12.1 The recommended concentration range is from 0.02 to0.10 mg of
20、 chromium per 250 mL of solution, using a 2-cmcell.NOTE 1This test method has been written for cells having a 2-cmlight path. Cells having other dimensions may be used, provided suitableadjustments can be made in the amounts of sample and reagents used.13. Stability of Color13.1 The color of the chr
21、omium complex develops almostimmediately but starts to fade after about 10 min. Photometricmeasurements should be made within 5 min after developingthe color.14. Interferences14.1 The elements ordinarily present do not interfere if theirconcentrations are under the maximum limits shown in 1.1.15. Re
22、agents15.1 Acetone (CH3COCH3).15.2 Ammonium Peroxydisulfate Solution (100 g/L)Dissolve 10 g of ammonium peroxydisulfate (NH4)2S2O8)inwater and dilute to 100 mL. Do not use a solution that hasstood more than 12 h.15.3 Chromium, Standard Solution (1 mL = 0.005 mg Cr)Dissolve 0.2830 g of potassium dich
23、romate (K2Cr2O7) in waterin a 1-L volumetric flask, dilute to volume, and mix. Using apipet, transfer 5 mL to a 100-mL volumetric flask, dilute tovolume, and mix.15.4 Diphenylcarbazide Solution (5 g/L)Dissolve 0.50 gof diphenylcarbazide (1,5-diphenylcarbohydrazide) in 100 mLof acetone. Do not use a
24、solution that has stood for more than1h.15.5 Phosphoric Acid (1 + 1)Mix 1 volume of concen-trated phosphoric acid (H3PO4, sp gr 1.69) with 1 volume ofwater.15.6 Silver Nitrate Solution (2.5 g/L)Dissolve 0.25 g ofsilver nitrate (AgNO3) in water and dilute to 100 mL.15.7 Sodium Hydroxide Solution (500
25、 g/LDissolve 50 gof sodium hydroxide (NaOH) in water, and dilute to 100 mL.15.8 Sulfuric Acid (1 + 1)Mix carefully and with stirring1 volume of concentrated sulfuric acid (H2SO4, sp gr 1.84) into1 volume of water.15.9 Purity of WaterUnless otherwise indicated, referenceto water shall be understood t
26、o mean reagent water as definedby Type II of Specification D 1193.16. Preparation of Calibration Curve16.1 Calibration Solutions:16.1.1 Using pipets, transfer 5, 10, 15, and 20 mL ofchromium solution (1 mL = 0.005 mg Cr) to 400-mL beakers.Add1mLofH3PO4(1 + 1) and dilute to approximately 250mL with w
27、ater.16.1.2 Adjust the pH to 0.95 6 0.05 with NaOH solution orH2SO4(1 + 1). Add 10 mL of AgNO3solution, 10 mL of(NH4)2S2O8solution, and a few glass beads. Cover the beakerwith a ribbed cover glass, and boil for at least 25 min. Duringthis period, add water as required to maintain a volume not lessth
28、an 150 mL. Cool, and transfer to a 250-mL volumetric flask.Proceed as directed in 16.3.16.2 Reference SolutionAdd1mLofH3PO4(1 + 1) to 250mL of water in a 400-mL beaker. Proceed as directed in 16.1.2.16.3 Color DevelopmentAdd 2.0 mL of diphenylcarba-zide solution. Dilute to volume, and mix.16.3.1 Pre
29、pare only that number of solutions which can bemeasured 5 min after color development.16.4 Photometry:16.4.1 Multiple-Cell PhotometerMeasure the cell correc-tion, using absorption cells with a 2-cm light path and a lightband centered at approximately 540 nm. Using the test cell,take the photometric
30、readings of the calibration solutions.16.4.2 Single-Cell PhotometerTransfer a suitable portionof the reference solution to an absorption cell with a 2-cm lightpath and adjust the photometer to the initial setting using a lightband centered at approximately 540 nm. While maintainingthis adjustment, t
31、ake the photometric readings of the calibra-tion solutions.E 439 04a216.5 Calibration CurvePlot the net photometric readingsof the calibration solutions against milligrams of chromium per250 mL of solution.17. Procedure17.1 Test Solution:17.1.1 Transfer a 0.50-g sample, weighed to the nearest 0.1mg,
32、 to a 250-mL beaker (Note 2). Add 100 mL of water and,in small increments, add 15 mL of H2SO4(1 + 1). Whenapparent reaction has ceased, warm until all action stops.NOTE 2If the chromium content of the sample is between 0.02 and0.04 %, use a 0.25-g sample.17.1.2 Filter through an 11-cm fine filter pa
33、per into a400-mL beaker. Wash the paper five or six times with hotwater. Reserve the filtrate. Transfer the paper to a platinumcrucible, dry, and ignite at 700C.17.1.3 Treat the residue with 1 drop of H2SO4(1+1),3or4drops of HNO3, and 3 or 4 mL of HF. Evaporate to completedryness, and ignite for 3 t
34、o 4 min at 900C. Fuse the residuewith about1gofpotassium pyrosulfate (K2S2O7). Cool, leachin 25 mL of water, add this solution to the reserved filtrate(17.1.2), and dilute to 250 mL. Proceed as directed in 16.1.2.17.2 Reference SolutionCarry a reagent blank through theentire procedure, using the sam
35、e amounts of all reagents withthe sample omitted for use as the reference solution.17.3 Color DevelopmentProceed as directed in 16.3.17.4 PhotometryTake the photometric reading of the testsolution as directed in 16.4.18. Calculation18.1 Convert the net photometric reading of the test solutionto mill
36、igrams of chromium by means of the calibration curve.Calculate the percentage of chromium as follows:Chromium, % 5 A/B 3 10! (1)where:A = chromium found in 250 mL of the final test solution,mg, andB = sample represented in 250 mL of the final test solution,g.19. Precision and Bias19.1 PrecisionEight
37、 cooperators from seven laboratoriescooperated in testing this test method and obtained the datasummarized in Table 1.19.2 BiasNo certified reference materials suitable fortesting this test method were available when this interlabora-tory testing program was conducted. The user of this standardis en
38、couraged to employ accepted reference materials, ifavailable, to determine the bias of this test method as appliedin a specific laboratory.19.3 E 173 has been replaced by Practice E 1601. TheReproducibility Index R2corresponds to the ReproducibilityIndex R of Practice E 1601. Likewise the Repeatabil
39、ity IndexR1corresponds to the Repeatability Index r of Practice E 1601.IRON BY THE 1,10-PHENANTHROLINEPHOTOMETRIC TEST METHOD20. Scope20.1 This test method covers the determination of iron inconcentrations from 0.05 to 0.25 %.21. Summary of Test Method21.1 The iron is reduced with hydroxylamine hydr
40、ochlorideand converted to the 1,10-phenanthroline complex. Photomet-ric measurement is made at approximately 515 nm.22. Concentration Range22.1 The recommended concentration range is from 0.05 to0.250 mg of iron per 100 mL of solution using a 2-cm cell.NOTE 3This test method has been written for cel
41、ls having a 2-cmlight path. Cells having other dimensions may be used, provided suitableadjustments can be made in the amounts of sample and reagents used.23. Stability of Color23.1 The color develops within 10 min and is stable for atleast 2 h.24. Interferences24.1 Nickel forms a complex with and c
42、onsumes 1,10-phenanthroline. However, an amount of nickel equivalent tofour times the amount of iron does not affect the irondetermination. Other elements ordinarily present in berylliumdo not interfere if their concentrations are under the maximumlimits shown in 1.1.25. Reagents25.1 Ammonium Acetat
43、e Solution (230/L)Dissolve 115 gof ammonium acetate in water and dilute to 500 mL.25.2 Hydroxylamine Hydrochloride Solution (100 g/L)Dissolve 5.0 g of hydroxylamine hydrochloride (NH2OH HCl) in 50 mL of water. Prepare fresh as needed.25.3 Iron, Standard Solution (1 mL = 0.01 mg Fe)Dissolve 0.7020 g
44、of ferrous ammonium sulfate(Fe(NH4)2(SO4)26H2O) in 10 mL of water, and add 1 mL ofH2SO4(1 + 1). Transfer to a 100-mL volumetric flask, dilute tovolume, and mix.25.4 1,10-Phenanthroline Solution (1 g/L)Dissolve 0.1 gof 1,10-phenanthroline monohydrate in 100 mL of water.25.5 Purity of WaterUnless othe
45、rwise indicated, referenceto water shall be understood to mean reagent water as definedby Type II of Specification D 1193.26. Preparation of Calibration Curve26.1 Calibration SolutionsUsing pipets, transfer 5, 10,15, 20, and 25 mL of iron solution (1 mL = 0.01 mg Fe) to100-mL volumetric flasks. Add
46、1 mL of H2SO4(1 + 1) anddilute to 50 mL. Proceed as directed in 26.3.TABLE 1 Statistical InformationTest MaterialChromiumFound, %Repeatability(R1, E 173)Reproducibility(R2, E 173)1 0.007 less than 0.001 0.0012 0.020 0.002 0.003E 439 04a326.2 Reference SolutionTransfer 50 mL of water and 1mL of H2SO4
47、(1 + 1) to a 100-mL volumetric flask. Proceed asdirected in 26.3.26.3 Color DevelopmentAdd3mLofNH2OH HClsolution, and 20 mL of ammonium acetate solution, and mix.Add 10 mL of 1,10-phenanthroline solution, and mix. Checkthe pH of the solution with indicator paper and, if required, addammonium acetate
48、 solution to adjust the pH to between 4.0 and4.5. Dilute to volume, and mix.26.4 Photometry:26.4.1 Multiple-Cell PhotometerDetermine the cell cor-rection using absorption cells with a 2-cm light path and a lightband centered at approximately 515 nm. Using the test cell,take the photometric readings
49、of the calibration solutions.26.4.2 Single-Cell PhotometerTransfer a suitable portionof the reference solution to an absorption cell with a 2-cm lightpath and adjust the photometer to the initial setting, using alight band centered at approximately 515 nm. While maintain-ing this adjustment, take the photometric readings of thecalibration solutions.26.5 Calibration CurvePlot the net photometric readingsof the calibration solutions against milligrams of iron per 100mL of solution.27. Procedure27.1 Test Solution:27.1.1 Transfer a 1.0-g
